CN111566154A - Foamable acrylic composition - Google Patents
Foamable acrylic composition Download PDFInfo
- Publication number
- CN111566154A CN111566154A CN201880076780.4A CN201880076780A CN111566154A CN 111566154 A CN111566154 A CN 111566154A CN 201880076780 A CN201880076780 A CN 201880076780A CN 111566154 A CN111566154 A CN 111566154A
- Authority
- CN
- China
- Prior art keywords
- meth
- acrylic
- fibers
- foamed
- article
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims abstract description 121
- 239000000203 mixture Substances 0.000 title claims description 44
- 238000000034 method Methods 0.000 claims abstract description 55
- 239000007788 liquid Substances 0.000 claims abstract description 54
- 239000000178 monomer Substances 0.000 claims abstract description 46
- 239000006260 foam Substances 0.000 claims abstract description 38
- 239000002131 composite material Substances 0.000 claims abstract description 33
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 21
- 238000005187 foaming Methods 0.000 claims abstract description 19
- 229920000103 Expandable microsphere Polymers 0.000 claims abstract description 18
- 230000009467 reduction Effects 0.000 claims abstract description 18
- 239000002666 chemical blowing agent Substances 0.000 claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 16
- 239000011347 resin Substances 0.000 claims abstract description 15
- 229920005989 resin Polymers 0.000 claims abstract description 14
- 238000000465 moulding Methods 0.000 claims abstract description 10
- 238000005266 casting Methods 0.000 claims abstract description 5
- 239000000835 fiber Substances 0.000 claims description 59
- 239000006188 syrup Substances 0.000 claims description 41
- 235000020357 syrup Nutrition 0.000 claims description 41
- 239000004604 Blowing Agent Substances 0.000 claims description 33
- 229920000642 polymer Polymers 0.000 claims description 30
- 229920001169 thermoplastic Polymers 0.000 claims description 30
- 239000004416 thermosoftening plastic Substances 0.000 claims description 29
- 239000003999 initiator Substances 0.000 claims description 22
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical group COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 20
- 239000011159 matrix material Substances 0.000 claims description 17
- 229920000058 polyacrylate Polymers 0.000 claims description 17
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 15
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 239000002657 fibrous material Substances 0.000 claims description 11
- 239000003365 glass fiber Substances 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000002557 mineral fiber Substances 0.000 claims description 8
- 238000009755 vacuum infusion Methods 0.000 claims description 8
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 7
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 6
- 239000004088 foaming agent Substances 0.000 claims description 6
- 210000004209 hair Anatomy 0.000 claims description 6
- 230000000977 initiatory effect Effects 0.000 claims description 6
- 239000002105 nanoparticle Substances 0.000 claims description 6
- 230000002787 reinforcement Effects 0.000 claims description 6
- 238000001721 transfer moulding Methods 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- -1 polyethylene Polymers 0.000 claims description 5
- 239000004800 polyvinyl chloride Substances 0.000 claims description 5
- ASRMWYDEZPXXBA-UHFFFAOYSA-N (sulfonylamino)urea Chemical compound NC(=O)NN=S(=O)=O ASRMWYDEZPXXBA-UHFFFAOYSA-N 0.000 claims description 4
- 244000198134 Agave sisalana Species 0.000 claims description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 4
- 244000025254 Cannabis sativa Species 0.000 claims description 4
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 claims description 4
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 claims description 4
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 4
- 244000060011 Cocos nucifera Species 0.000 claims description 4
- 235000013162 Cocos nucifera Nutrition 0.000 claims description 4
- 240000000491 Corchorus aestuans Species 0.000 claims description 4
- 235000011777 Corchorus aestuans Nutrition 0.000 claims description 4
- 235000010862 Corchorus capsularis Nutrition 0.000 claims description 4
- 229920000742 Cotton Polymers 0.000 claims description 4
- 241000196324 Embryophyta Species 0.000 claims description 4
- 241000219146 Gossypium Species 0.000 claims description 4
- 240000006240 Linum usitatissimum Species 0.000 claims description 4
- 235000004431 Linum usitatissimum Nutrition 0.000 claims description 4
- 241001465754 Metazoa Species 0.000 claims description 4
- 235000018290 Musa x paradisiaca Nutrition 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 4
- 229920002522 Wood fibre Polymers 0.000 claims description 4
- 229910052796 boron Inorganic materials 0.000 claims description 4
- 235000009120 camo Nutrition 0.000 claims description 4
- 239000004917 carbon fiber Substances 0.000 claims description 4
- 235000005607 chanvre indien Nutrition 0.000 claims description 4
- 239000011487 hemp Substances 0.000 claims description 4
- VYFOAVADNIHPTR-UHFFFAOYSA-N isatoic anhydride Chemical compound NC1=CC=CC=C1CO VYFOAVADNIHPTR-UHFFFAOYSA-N 0.000 claims description 4
- HWPKGOGLCKPRLZ-UHFFFAOYSA-M monosodium citrate Chemical compound [Na+].OC(=O)CC(O)(C([O-])=O)CC(O)=O HWPKGOGLCKPRLZ-UHFFFAOYSA-M 0.000 claims description 4
- 229920000647 polyepoxide Polymers 0.000 claims description 4
- 229920000728 polyester Polymers 0.000 claims description 4
- 229920000573 polyethylene Polymers 0.000 claims description 4
- 229920000098 polyolefin Polymers 0.000 claims description 4
- 239000004814 polyurethane Substances 0.000 claims description 4
- 229920002635 polyurethane Polymers 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 238000005507 spraying Methods 0.000 claims description 4
- 229920006305 unsaturated polyester Polymers 0.000 claims description 4
- 229920001567 vinyl ester resin Polymers 0.000 claims description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 4
- 239000002025 wood fiber Substances 0.000 claims description 4
- 210000002268 wool Anatomy 0.000 claims description 4
- CZGWDPMDAIPURF-UHFFFAOYSA-N (4,6-dihydrazinyl-1,3,5-triazin-2-yl)hydrazine Chemical compound NNC1=NC(NN)=NC(NN)=N1 CZGWDPMDAIPURF-UHFFFAOYSA-N 0.000 claims description 3
- BLJHFERYMGMXSC-UHFFFAOYSA-N 3-[3-(hydrazinesulfonyl)phenyl]sulfonylbenzenesulfonohydrazide Chemical compound NNS(=O)(=O)C1=CC=CC(S(=O)(=O)C=2C=C(C=CC=2)S(=O)(=O)NN)=C1 BLJHFERYMGMXSC-UHFFFAOYSA-N 0.000 claims description 3
- ICGLPKIVTVWCFT-UHFFFAOYSA-N 4-methylbenzenesulfonohydrazide Chemical compound CC1=CC=C(S(=O)(=O)NN)C=C1 ICGLPKIVTVWCFT-UHFFFAOYSA-N 0.000 claims description 3
- MARUHZGHZWCEQU-UHFFFAOYSA-N 5-phenyl-2h-tetrazole Chemical compound C1=CC=CC=C1C1=NNN=N1 MARUHZGHZWCEQU-UHFFFAOYSA-N 0.000 claims description 3
- 239000004156 Azodicarbonamide Substances 0.000 claims description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 3
- VRFNYSYURHAPFL-UHFFFAOYSA-N [(4-methylphenyl)sulfonylamino]urea Chemical compound CC1=CC=C(S(=O)(=O)NNC(N)=O)C=C1 VRFNYSYURHAPFL-UHFFFAOYSA-N 0.000 claims description 3
- 229960004543 anhydrous citric acid Drugs 0.000 claims description 3
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 claims description 3
- 235000019399 azodicarbonamide Nutrition 0.000 claims description 3
- 229910052788 barium Inorganic materials 0.000 claims description 3
- 229960004106 citric acid Drugs 0.000 claims description 3
- 235000015165 citric acid Nutrition 0.000 claims description 3
- 239000011370 conductive nanoparticle Substances 0.000 claims description 3
- 238000009730 filament winding Methods 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 239000004953 Aliphatic polyamide Substances 0.000 claims description 2
- 229920003231 aliphatic polyamide Polymers 0.000 claims description 2
- 239000004760 aramid Substances 0.000 claims description 2
- 229920003235 aromatic polyamide Polymers 0.000 claims description 2
- 238000007766 curtain coating Methods 0.000 claims description 2
- 239000003822 epoxy resin Substances 0.000 claims description 2
- 238000007755 gap coating Methods 0.000 claims description 2
- 238000007756 gravure coating Methods 0.000 claims description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000007758 immersion dip coating Methods 0.000 claims description 2
- 238000007764 slot die coating Methods 0.000 claims description 2
- 240000008790 Musa x paradisiaca Species 0.000 claims 1
- 239000004372 Polyvinyl alcohol Substances 0.000 claims 1
- 239000004005 microsphere Substances 0.000 abstract description 28
- 230000008569 process Effects 0.000 abstract description 16
- 238000001125 extrusion Methods 0.000 abstract description 4
- 230000003287 optical effect Effects 0.000 abstract description 4
- 238000000071 blow moulding Methods 0.000 abstract description 2
- 238000012662 bulk polymerization Methods 0.000 abstract description 2
- 238000010128 melt processing Methods 0.000 abstract description 2
- 238000004382 potting Methods 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 12
- 239000002245 particle Substances 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 10
- 229920001577 copolymer Polymers 0.000 description 9
- 238000009826 distribution Methods 0.000 description 7
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 7
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 6
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 6
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 6
- 239000004926 polymethyl methacrylate Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 5
- 229910000831 Steel Inorganic materials 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 239000010959 steel Substances 0.000 description 5
- 229920001519 homopolymer Polymers 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 3
- 229920000178 Acrylic resin Polymers 0.000 description 3
- 241000234295 Musa Species 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000002390 adhesive tape Substances 0.000 description 3
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 3
- 150000003254 radicals Chemical group 0.000 description 3
- 229920001187 thermosetting polymer Polymers 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- 239000006057 Non-nutritive feed additive Substances 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 229920005830 Polyurethane Foam Polymers 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 229920006243 acrylic copolymer Polymers 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
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- 230000015556 catabolic process Effects 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
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- 239000004794 expanded polystyrene Substances 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
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- 238000005470 impregnation Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
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- LWIHDJKSTIGBAC-UHFFFAOYSA-K potassium phosphate Substances [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 2
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- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 1
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
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- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 description 1
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- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 1
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 description 1
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- 238000007598 dipping method Methods 0.000 description 1
- 238000004100 electronic packaging Methods 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
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- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/10—Homopolymers or copolymers of methacrylic acid esters
- C08L33/12—Homopolymers or copolymers of methyl methacrylate
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
- B29C44/34—Auxiliary operations
- B29C44/3415—Heating or cooling
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
- B29C44/34—Auxiliary operations
- B29C44/36—Feeding the material to be shaped
- B29C44/38—Feeding the material to be shaped into a closed space, i.e. to make articles of definite length
- B29C44/44—Feeding the material to be shaped into a closed space, i.e. to make articles of definite length in solid form
- B29C44/445—Feeding the material to be shaped into a closed space, i.e. to make articles of definite length in solid form in the form of expandable granules, particles or beads
-
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- C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
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Abstract
The present invention relates to foamed acrylic materials using conventional chemical blowing agents and foamable microspheres. Acrylic foams have improved density reduction, optical properties and insulating properties. The acrylic foam of the present invention can be formed by conventional melt processing methods (extrusion, blow molding, etc.) as well as innovative foaming methods (e.g., foaming during or after polymerization). One novel method of the present invention involves the use of expandable microspheres in admixture with monomers which are then polymerized by bulk polymerization in a cell casting, potting or molding process. The process can be used effectively to produce composite foam structures, for example, with those from the company arkema
The liquid resin is combined.
Description
Technical Field
The present invention relates to foamed acrylic materials using conventional chemical blowing agents and foamable microspheres. Acrylic foams have improved density reduction, optical properties and insulating properties. The acrylic foam of the present invention can be formed by conventional melt processing methods (extrusion, blow molding, etc.) as well as innovative foaming methods (e.g., foaming during or after polymerization). One novel method of the present invention involves the use of expandable microspheres blended with monomers, which are then polymerized by bulk polymerization in a cell cast, pour, or molding process. The present invention is effective in producing a composite foam structure.
Background
Traditionally, foamed polymers are produced using chemical or physical blowing agents. In the case of chemical blowing agents, the gas is generated by heating the chemical above its degradation temperature to effect decomposition. In the case of physical blowing agents, the gas is introduced directly into the polymer or by heating the liquid blowing agent above its evaporation temperature to cause it to evaporate. Although the batch process uses primarily physical blowing agents, either type of blowing agent can be used in either the continuous or batch foaming process. Chemical blowing agents are used primarily for higher density foams (down to 50% density reduction), while physical blowing agents can produce light foams-up to 10 times density reduction.
Currently available expanded plastic sheet products include expanded PVC, expanded polystyrene, and aluminum composites. When a temperature change occurs due to a high internal stress, the foamed PVC tends to warp and is poor in weather resistance. The expanded polystyrene has dents on the surface. Aluminum composites can often delaminate and have poor printability. Due to the deficiencies of foamed PVC, foamed polystyrene and aluminum composites, the market demands foamed acrylic materials.
Acrylic is a preferred thermoplastic material over other plastics due to excellent weatherability, gloss surface and printability. There is a need for foamed acrylic materials for use on an industrial scale.
More recently, new methods have been developed for foaming amorphous and semi-crystalline polymers in the form of expandable microspheres. US7879441 describes a foamed article prepared by adding expandable microspheres to a polymer matrix in an extruder. The mixture may be expanded in an extruder-producing a foamed article, or may remain relatively unexpanded and foamed in situ. The application is mainly for adhesive tapes. US 2015/0322226 also describes the use of microspheres for foaming polymers.
Microspheres are small hollow particles with a polymeric shell that can encapsulate various liquids or gases. Upon heating, the polymer shell softens and the liquid within the sphere evaporates, generating a large volume of high pressure gas-which will cause the microspheres to expand significantly. The spheres can be of various diameters (typically with a broad size distribution), shell thicknesses, shell compositions (typically lightly crosslinked acrylates, methacrylates, and copolymers thereof with acrylonitrile), and can contain various liquids or gases (typically isooctane, isobutylene, isopentane, or mixtures thereof). The microspheres may additionally comprise finely dispersed organic or non-organic materials on the surface and inside the surface. Microspheres are generally available from many manufacturers in a wide range of particle sizes and distributions. Typically, the microspheres have an average particle size of less than 10 microns before expansion and a shell thickness of a few microns, while the average particle size after expansion is tens of microns with a shell thickness of less than one micron.
Durable, strong, lightweight materials are needed to replace steel and other metals. Recently, the Arkema company has introduced an acrylic/fiber composite thermoplastic material formed from a (meth) acrylic monomer/(meth) acrylic polymer/initiator liquid blend and long fibers, as described in US 9,777,140. These strong materials have the appearance and weatherability of acrylics, but unlike typical thermoset composites, thermoplastic acrylic composites can be thermoformed and recycled.
Summary of The Invention
The present invention relates to (meth) acrylic foams and foam composites, including novel production and foaming processes.
Within this specification, embodiments have been described in a manner that enables a clear and concise specification to be written, but it is intended and will be understood that various combinations and subcombinations of the embodiments may be made without departing from the invention. For example, it should be understood that all of the preferred features described herein apply to all of the aspects of the invention described herein.
Aspects of the invention include:
1. a polymer foam composite comprising:
(a) a foamed polymeric thermoplastic (meth) acrylic matrix;
(b) the fibrous material used as a reinforcement is,
wherein the fibrous material comprises fibers having a fiber aspect ratio of at least 1000 or a fibrous material having a two-dimensional macrostructure, wherein the density of the foamed polymeric thermoplastic (meth) acrylic matrix is at least 5 wt. -%, preferably 10 wt. -%, preferably 20 wt. -%, preferably 30 wt. -%, more preferably 50 wt. -%, more preferably 70 wt. -%, more preferably 90 wt. -% lower than that of an unfoamed polymeric thermoplastic (meth) acrylic matrix of the same composition.
2. The polymer foam composite of aspect 1, wherein the fibers are selected from the group consisting of: natural materials, plant fibers, wood fibers, animal fibers, mineral fibers, sisal, jute, hemp, flax, cotton, coconut fibers, banana fibers, wool, hair (hair), aliphatic polyamides, aromatic polyamides, polyesters, polyvinyl alcohols, polyolefins, polyurethanes, polyvinyl chloride, polyethylene, unsaturated polyesters, epoxy resins, vinyl esters, mineral fibers, glass fibers, carbon fibers, boron fibers, silica fibers.
3. The polymer foamed composite of any of aspects 1 and 2, wherein the (meth) acrylic matrix polymer comprises at least 70% by weight methyl methacrylate monomer units.
4. The polymer foamed composite of any of aspects 1-3, further comprising 0.1 to 10 wt% of remaining expandable microspheres based on the weight of the polymeric thermoplastic (meth) acrylic matrix.
5. A liquid (meth) acrylic syrup comprising:
a) a (meth) acrylic polymer;
b) a (meth) acrylic monomer;
c) at least one initiator or initiating system to initiate polymerization of the (meth) acrylic monomer;
d) at least one kind of foaming agent,
the dynamic viscosity of the liquid (meth) acrylic syrup ranges from 10 to 10000, preferably from 50 to 5000, and advantageously from 100 to 1000mPa s.
6. The liquid (meth) acrylic syrup of aspect 5, wherein the blowing agent comprises at least one chemical blowing agent.
7. The liquid (meth) acrylic syrup of any of aspects 5 and 6, wherein the chemical blowing agent is selected from the group consisting of: azodicarbonamide, azobisisobutyronitrile, sulfonyl semicarbazide (sulfonylsemicarbazide), 4-hydroxybenzene, barium azodicarboxylate, 5-phenyltetrazole, p-toluenesulfonyl semicarbazide, diisopropyliminodicarboxylate, 4' -oxybis (benzenesulfonylhydrazide), diphenylsulfone-3, 3' -disulfonylhydrazide, isatoic anhydride (isatoic anhydride), N ' -dimethyl-N, N ' -dinitroterephthalamide, citric acid, sodium bicarbonate, monosodium citrate, anhydrous citric acid, trihydrazinotriazine, N ' -dinitrosopentamethylenetetramine, p-toluenesulfonylhydrazide and blends thereof.
8. The liquid (meth) acrylic syrup of any of aspects 5 to 7, wherein the foaming agent comprises expandable microspheres.
9. A thermoplastic (meth) acrylic foamed article comprising a (meth) acrylic matrix, the foamed article having a density reduction of at least 33%, at least 75%, at least 90% compared to an unfoamed (meth) acrylic article of the same composition.
10. The thermoplastic (meth) acrylate foamed article of aspect 9 comprising a thermoplastic (meth) acrylate matrix containing 0.1 to 10 wt%, preferably 1 to 5 wt% nanoparticles.
11. The thermoplastic (meth) acrylate foamed article of any one of aspects 9 and 10, wherein the nanoparticles are conductive nanoparticles.
12. The thermoplastic (meth) acrylate foamed article of any one of aspects 9 to 11, comprising a (meth) acrylic sheet having a k-factor at 25 ° f of less than 0.7, preferably less than 0.5, more preferably less than 0.25.
13. The thermoplastic (meth) acrylate foamed article of any one of aspects 9 to 12 having a class a surface as determined by ASTM E340.
14. A method for foaming a (meth) acrylic foam, the method comprising the steps of:
a. admixing a blowing agent, a (meth) acrylic monomer, a (meth) acrylic polymer, and one or more initiators to form a liquid (meth) acrylic syrup having a dynamic viscosity in the range of from 10 mPas to 10000 mPas, preferably from 50 mPas to 5000 mPas, and advantageously from 100 mPas to 1000 mPas,
b. the structure is formed by polymerization of a liquid (meth) acrylic syrup.
15. The method of aspect 14, wherein the foaming and the polymerization process occur simultaneously to form the foamed structure.
16. The method of any of aspects 14 or 15, wherein the structure is foamed after polymerization by adding energy capable of expanding a blowing agent.
17. The method of any of aspects 14-16, wherein the blowing agent comprises at least one chemical blowing agent.
18. The method of any of aspects 14-17, wherein the foaming agent comprises expandable microspheres.
19. The method of any of aspects 14 to 18, wherein the structure formation is performed by cell casting, solid state casting, vacuum infusion, pultrusion, wet molding, resin transfer molding, compressed resin transfer molding, lay-up/spraying, or filament winding.
20. The method of any of aspects 14 to 19, wherein the liquid (meth) acrylic syrup is combined with long fibers or fibrous materials having a two-dimensional or three-dimensional macrostructure with a fiber aspect ratio of at least 1000 prior to polymerization.
21. The method of any one of aspects 14 to 20, wherein the combining of long fibers with liquid (meth) acrylic syrup is achieved by gravure coating, immersion dip coating (immersion painting), slot die coating, curtain coating, or gap coating.
22. A method for forming a (meth) acrylic foam having an improved surface appearance as determined by ASTM E340, comprising the steps of:
a) forming a thermoplastic (meth) acrylic foamed article in a mold, wherein the thermoplastic (meth) acrylic foamed article comprises expandable microspheres;
b) curing the article;
c) enlarging the size of the mold by slightly opening the mold or moving the cured article into a slightly larger mold;
d) adding additional heat to the article, causing it to expand further to fill the larger mold;
e) allowing the article to cool; and
f) the article is demolded.
23. The polymer foamed composite of aspect 1, wherein the material is an article for use as an automotive part, a ship part, a train part, a sporting article, an airplane part, a helicopter part, a spacecraft part, a rocket part, a photovoltaic module part, a wind turbine part, a furniture part, a structural part, a building part, a telephone or cell phone part, a computer or television part, a printer part, or a photocopy part.
Drawings
FIG. 1 shows two molded parts of the invention, the left part being formed by conventional compression molding as in example 3. The right hand part was formed by the process of example 4 to obtain a "class a" surface.
Detailed Description
Problems to be solved: it is desirable to produce acrylic foams having improved density reduction, excellent optical properties and/or good insulating properties. There is also a need for a foamed acrylic composite having the advantages of a thermoplastic acrylic composite having a higher strength to weight ratio by reducing density while maintaining sufficient mechanical properties.
The solution is as follows: acrylic foams have now been formed by incorporating blowing agents into liquid acrylic syrup that can subsequently be polymerized and foamed. Foaming can occur during or after polymerization, providing production flexibility as well as improvements in optical and/or mechanical properties. Acrylic foams can be combined with long fibers to form composites having improved strength to weight ratios, weldability, thermoformability, and recyclability.
As used herein, "copolymer" refers to a polymer having two or more different monomer units. "Polymer" is used to denote both homopolymers and copolymers. For example, "PMMA" and "polymethylmethacrylate" as used herein are used to refer to homopolymers and copolymers unless specifically stated otherwise. (meth) acrylate is used to denote both acrylate and methacrylate, and mixtures of the two. The polymers may be linear, branched, star-shaped, comb-shaped, block-shaped or any other structure. The polymer may be homogeneous, heterogeneous, and may have a gradient distribution of comonomer units. All references cited are incorporated herein by reference.
As used herein, percentages shall refer to weight percentages unless otherwise indicated. Molecular weight is the weight average molecular weight as determined by GPC when the polymer contains some cross-links, GPC cannot be employed due to insoluble polymer fraction, soluble fraction/gel fraction or soluble fraction molecular weight after extraction from gel is used.
Liquid acrylic resin:
the liquid acrylic resin of the present invention, also referred to as a liquid acrylic syrup, is a viscous polymerizable blend of a (meth) acrylic polymer, a (meth) acrylic monomer, and an initiator.
(meth) acrylic polymer: in one embodiment, the (meth) acrylic polymer comprises at least 70% by weight of methyl methacrylate.
In another embodiment, PMMA is a mixture of at least one copolymer of MMA with at least one homopolymer, or a mixture of at least two copolymers or at least two homopolymers of MMA with different average molecular weights, or a mixture of at least two copolymers of MMA with different monomer compositions.
A copolymer of Methyl Methacrylate (MMA) comprises 70 to 99.7 wt% methyl methacrylate and 0.3 to 30 wt% of at least one monomer having at least one ethylenically unsaturated group (ethylene unsaturation) that is copolymerizable with methyl methacrylate.
These monomers are well known and mention may in particular be made of acrylic acid and methacrylic acid and alkyl (meth) acrylates whose alkyl group has from 1 to 12 carbon atoms. For example, mention may be made of methyl acrylate and ethyl (meth) acrylate, butyl (meth) acrylate or 2-ethylhexyl (meth) acrylate. Preferably, the comonomer is an alkyl acrylate with an alkyl group having 1 to 4 carbon atoms.
In a preferred embodiment, the copolymer of Methyl Methacrylate (MMA) comprises from 70% to 99.7%, preferably from 80% to 99.7%, advantageously from 90% to 99.7%, more advantageously from 90% to 99.5% by weight of methyl methacrylate and from 0.3% to 30%, preferably from 0.3% to 20%, advantageously from 0.3% to 10%, and more advantageously from 0.5% to 10% by weight of at least one monomer having at least one ethylenically unsaturated group which is copolymerizable with methyl methacrylate. Preferably, the comonomer is selected from: methyl acrylate, ethyl acrylate, or mixtures thereof.
The weight average molecular weight of the (meth) acrylic polymer should be high, meaning greater than 50,000 g/mole, preferably greater than 100,000 g/mole.
The weight average molecular weight can be determined by Size Exclusion Chromatography (SEC).
(methacrylic) monomer: the (meth) acrylic polymer is dissolved in one or more (meth) acrylic monomers. One or more monomers are selected from: acrylic acid, methacrylic acid, an alkyl acrylic monomer, an alkyl methacrylic monomer, or mixtures thereof.
Preferably, the monomer is selected from: acrylic acid, methacrylic acid, alkyl acrylic monomers, alkyl methacrylic monomers, and mixtures thereof, the alkyl group having from 1 to 22 carbon atoms and being straight, branched, or cyclic; preferably, the alkyl group has 1 to 12 carbon atoms and is straight, branched or cyclic.
Advantageously, the (meth) acrylic monomer is chosen from: methyl methacrylate, ethyl methacrylate, methyl acrylate, ethyl acrylate, methacrylic acid, acrylic acid, n-butyl acrylate, isobutyl acrylate, n-butyl methacrylate, isobutyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, isobornyl acrylate, isobornyl methacrylate, and mixtures thereof.
More advantageously, the monomers are selected from: (meth) acrylic monomers selected from methyl methacrylate, isobornyl acrylate or acrylic acid, and mixtures thereof.
In a preferred embodiment, at least 50% by weight of the monomer is methyl methacrylate.
In a more preferred embodiment, at least 50% by weight of the monomers are a mixture of methyl methacrylate and isobornyl acrylate and/or acrylic acid.
In view of the (meth) acrylic monomer and the (meth) acrylic polymer, the (meth) acrylic monomer or monomers in the liquid (meth) acrylic syrup make up at least 40 wt%, preferably 50 wt%, advantageously 60 wt%, more advantageously 65 wt% of the total liquid (meth) acrylic syrup.
The one or more (meth) acrylic monomers in the liquid (meth) acrylic syrup comprise up to 90 wt%, the one or more (meth) acrylic polymers in the liquid (meth) acrylic syrup comprise at least 10 wt%, and the one or more (meth) acrylic polymers in the liquid (meth) acrylic syrup comprise up to 60 wt%.
In view of the (meth) acrylic monomer and the (meth) acrylic polymer, the (meth) acrylic monomer or monomers in the liquid (meth) acrylic syrup account for 40 to 90% by weight, preferably 50 to 90% by weight, of the total liquid syrup.
Thus, in view of the (meth) acrylic monomer and the (meth) acrylic polymer, the one or more (meth) acrylic polymers in the liquid (meth) acrylic syrup account for 50 to 10 wt% of the total liquid syrup.
The dynamic viscosity of the liquid (meth) acrylic syrup ranges from 10 to 10000, preferably from 50 to 5000, and advantageously from 100 to 1000mPa s. The viscosity of the slurry can be readily determined with a rheometer or viscometer. The dynamic viscosity was measured at 25 ℃. The liquid (meth) acrylic syrup has newtonian behavior, which means no shear thinning, so that the dynamic viscosity is independent of the shear in the rheometer or the speed of movement in the viscometer.
Initiator: as the initiator and the initiation system for starting the polymerization of the (meth) acrylic monomer, an initiator or an initiation system activated by heat may be mentioned.
The thermally activated initiator is preferably a free radical initiator. Preferably, the initiator is selected from the following: diacyl peroxides, peroxyesters, dialkyl peroxides, peroxyacetals, or azo compounds.
Preferably, the initiator or initiator system for starting the polymerization of the (meth) acrylic monomers is chosen from peroxides having from 2 to 20 carbon atoms.
The content of the radical initiator is 100ppm to 50,000ppm by weight (50000ppm to 5% by weight), preferably 200ppm to 40,000ppm by weight, and advantageously 300ppm to 30000ppm by weight with respect to the (meth) acrylic monomer of the liquid (meth) acrylic syrup.
In one embodiment, an inhibitor is present to prevent spontaneous polymerization of the monomer.
Foaming agent: blowing agents useful in the present invention include chemical blowing agents as well as expandable microspheres.
The unexpanded microspheres are crosslinked acrylic copolymer (acrylonitrile and MMA) shells containing isopentane blowing agent. Isopentane boils upon heating, causing the shell to expand to 6-8 times its original size. An example of expandable microspheres is from Akzo Nobel
And (3) microspheres.
The expandable microspheres of the present invention are typically powders and may be present in unexpanded or expanded form. To extrude the foam from the polymer in granular form, it is more convenient to add the blowing agent also in granular form. It is therefore desirable to prepare a particulate concentrate or masterbatch containing microspheres by adding it to a polymeric carrier and using it for foam extrusion.
Forming a foam with expandable microspheres has several processing advantages. The interaction between the gas/polymer matrix is less and therefore there is less concern of a drop in melt strength due to dissolved gas. The compatibility of the foaming gas with the polymer, expressed in terms of its solubility, diffusivity and permeability, is of little concern. This allows cell formation (cellularization) and enlargement phenomena to be decoupled from the polymer/gas compatibility. The temperature profile of the extruder will be more similar to that used for neat polymer extrusion and the processing window is wider than the other two forms of foaming technology. The bubbles formed from the expanding gas generally do not collapse without coalescing into large voids, as can occur in the other two foaming techniques. The pore size distribution of the foam is a function of the particle size distribution of the microspheroidal particles. Thus, the combination of temperature and residence time of the process should be of particular interest, as maintaining the mixture at an elevated temperature for an extended period of time can result in the gas within the formed bubbles escaping from its thin shell into the polymer matrix where the bubbles can collapse. Temperature and residence time control of the process is critical to the formation of good closed foam. The microspheres do not require the addition of nucleating agents.
Microsphere formation may use a continuous or batch foaming process and may be expanded during or after polymerization of the (meth) acrylic syrup.
Chemical blowing agents may also be used in the (meth) acrylic syrup. Chemical blowing agents useful in the present invention include those that are compatible with (meth) acrylic acid and have similar degradation temperatures (220 ℃ to 240 ℃). In the case of chemical blowing agents, the gas is generated by heating the chemical above its decomposition temperature to effect decomposition. In the case of physical blowing agents, the gas is introduced directly into the polymer or by heating the liquid blowing agent above its evaporation temperature to cause it to evaporate. Chemical blowing agents are used primarily for higher density foams (down to 70% density reduction), while physical blowing agents can produce light foams-up to 10 times density reduction.
The chemical blowing agent may be a solid or a fluid. Useful blowing agents include, but are not limited to: azodicarbonamide, azobisisobutyronitrile, sulfonyl semicarbazide, 4-hydroxybenzene, barium azodicarboxylate, 5-phenyltetrazole, p-toluenesulfonyl semicarbazide, diisopropyliminodicarboxylate, 4' -oxybis (benzenesulfonylhydrazide), diphenylsulfone-3, 3' -disulfonylhydrazide, isatoic anhydride, N ' -dimethyl-N, N ' -dinitroterephthalamide, citric acid, sodium bicarbonate, monosodium citrate, anhydrous citric acid, trihydrazinotriazine, N ' -dinitrosopentamethylenetetramine, and p-toluenesulfonylhydrazide, or a blend comprising two or more of the blowing agents described. The invention also contemplates chemical blowing agents and/or mixtures of chemical and physical blowing agents
The blowing agent content may vary between 0.1-10% to achieve the target density reduction. When 0.5% monosodium citrate and 10% processing aid (PLASTICSTRENGTH p566, arkema) were used as blowing agents, a 40% density reduction was achieved in the foamed acrylic rod (PLEXIGLA V045 resin, arkema). Using 0.6% thiohydrazine derivative as blowing agent and 5% processing aid (Plastistrength P566), a 33% density reduction in acrylic foamed sheet (Plexiglas V045 resin) can be achieved. Acrylic sheets foamed with this method have a rough surface due to the wide distribution of bubble sizes. The pore size and surface properties can be improved by the following methods.
Other additives:
other optional additives may be part of the liquid (meth) acrylic syrup. These additives include: activators, fibers, colorants, fillers, carbon nanotubes or graphite oxide, nanoparticles for polymerization that can be added to the monomer/initiator/blowing agent mixture to achieve desired properties.
The content of the activator is 100ppm to 10,000ppm (by weight), preferably 200ppm to 7000ppm by weight, and advantageously 300ppm to 4000ppm with respect to the (meth) acrylic monomer of the liquid (meth) acrylic syrup.
In one embodiment, nanoparticles may be added to form a thermally or electrically conductive thermoplastic nanocomposite foam. In this case, dry unexpanded microspheres and (meth) acrylic liquid resin may be mixed with 1-20 wt.% conductive nanoparticles of appropriate aspect ratio (e.g., carbon nanotubes (GRAPHISTRENGTH, arkema corporation) or graphene, graphite nanoparticles, graphite oxide, or boron nitride. the mixture may be initiated and polymerized in a 1/8 "thick glass mold after heating the sheet at 180 ℃ for 15 minutes, which may expand. the surface of the spheres may be subjected to up to 10,000% biaxial strain given that the expandable microspheres expand up to 10 times their original diameter, creating a flow field between adjacent expanded spheres. Conductive foam is a desirable low density material.
In one embodiment, the liquid (meth) acrylic syrup of the present invention may be used to impregnate fibers. Impregnation may take place in a mould, for example by vacuum infusion or wet moulding, or by dipping, spraying or otherwise impregnating the long fibres with a liquid (meth) acrylic syrup. The impregnated fibers are then polymerized and foamed.
Fibrous substrates of the present invention include, but are not limited to: a mat, fabric, felt or nonwoven, which may be in the form of a strip, loop, knitted bundle, lock pin (lock) or block. The fibrous material may have various forms and dimensions in one, two or three dimensions. The fibrous base material comprises a collection of one or more fibers. When the fibers are continuous, they are assembled to form a fabric.
The one-dimensional form is a linear long fiber. The fibers may be discontinuous or continuous. The fibers may be arranged randomly or as continuous filaments that are parallel to each other. A fiber is defined by its aspect ratio, which is the ratio between the length and diameter of the fiber. The fibers used in the present invention are long fibers or continuous fibers. The aspect ratio of the fibres is at least 1000, preferably at least 1500, more preferably at least 2000, advantageously at least 3000, most preferably at least 5000.
The two-dimensional fibers may be fiber mats or non-woven reinforcements or woven rovings or fiber bundles, which may also be bundle-woven.
The three-dimensional forms are for example stacked or folded fibre mats or non-woven reinforcements or fibre bundles or mixtures thereof, the two-dimensional forms in the third dimension being assembled.
The fibrous material may be natural or synthetic. Natural materials include, but are not limited to: plant fibers, wood fibers, animal fibers or mineral fibers, for example sisal, jute, hemp, flax, cotton, coconut fibers, banana fibers, wool or hair (hair).
Synthetic materials include, but are not limited to: polymer fibers of a thermosetting or thermoplastic polymer, or mixtures thereof. These materials include: polyamides (aliphatic or aromatic), polyesters, polyvinyl alcohols, polyolefins, polyurethanes, polyvinyl chlorides, polyethylenes, unsaturated polyesters, epoxies, and vinyl esters.
Mineral fibers are a preferred embodiment and include glass fibers, particularly E-, R-or S2-type glass fibers; carbon fibers; boron fibers; or silica fibers.
In one embodiment, the liquid (meth) acrylic syrup of the present invention may be mixed with short fibers (e.g., short glass fibers), and then foamed and polymerized. In this case, impregnation of the fibres in the mould is not necessary. The aspect ratio of the fibres is below 5000, preferably below 3000, more preferably below 2000, advantageously below 1500, most advantageously below 1000.
The fibrous material may be natural or synthetic. Natural materials include, but are not limited to: plant fibers, wood fibers, animal fibers or mineral fibers, for example sisal, jute, hemp, flax, cotton, coconut fibers, banana fibers, wool or hair.
Synthetic materials include, but are not limited to: polymer fibers of a thermosetting or thermoplastic polymer, or mixtures thereof. These materials include: polyamides (aliphatic or aromatic), polyesters, polyvinyl alcohols, polyolefins, polyurethanes, polyvinyl chlorides, polyethylenes, unsaturated polyesters, epoxies, and vinyl esters.
Mineral fibers are a preferred embodiment and include glass fibers, particularly E-, R-or S2-type glass fibers; carbon fibers; boron fibers; or silica fibers.
The method comprises the following steps:
the blowing agent may be incorporated into the acrylic monomer and remain unexpanded, or it may expand in situ during polymerization.
The blowing agent of the present invention is added to the liquid (meth) acrylic syrup. The expandable microspheres are not added separately to the monomer, as a higher viscosity is required to form a stable suspension.
The blowing agent may be triggered during or after polymerization of the (meth) acrylic monomer. In one embodiment, the initiator may be selected such that the exotherm generated during polymerization simultaneously initiates and cures the foam.
In another embodiment, the liquid (meth) acrylic syrup may be polymerized followed by initiation of the blowing agent to produce the foam.
Foams and syntactic foams may be formed by typical processes including, but not limited to: vacuum infusion, wet molding, resin transfer molding, compression resin transfer molding, lay-up spraying, filament winding, and pultrusion.
In one embodiment, a multilayer structure is formed having at least one foamed layer of the present invention in combination with at least one unfoamed layer. This may be a foam-core structure in which the foam layer is formed between two layers of non-foamed material, which may be a (meth) acrylic layer or a compatible polymer such as styrene.
Some examples of the method of the present invention include the following examples. Other methods and variations of the present invention will readily occur to those of ordinary skill in the art based on the examples provided.
The liquid acrylic resin is 10 to 60% by weight of a (meth) acrylic polymer dissolved in 40 to 90% by weight of a (meth) acrylic monomer.
a) In one embodiment, the dried unexpanded is expanded
Microspheres 950DU80 were dispersed in a laboratory shaker
190 (f).
The mixture is 1%
16 initiation and polymerization was carried out in a water bath at 61 ℃ in an 1/8 "thick glass mold. An 1/8 "thick translucent sheet was obtained with a smooth and glossy surface.
After heating the sheet at 180 ℃ for 15 minutes, it expanded to 8-9 times its original volume. A90% reduction in density was obtained using 10% by weight of Expancel 950DU80 microspheres. It should be noted that the particles cannot remain dispersed in MMA because a certain viscosity is required to obtain a stable suspension and an Elium grade with a viscosity of 100cP can accommodate up to 10 wt.% of the particles.
The foamed PMMA sheet produced by this method has an incredibly uniform bubble size (108. + -.30 μm) and a bubble structure: there is no distinction between sheet surface/edge and sheet center. The 90% reduced density foam sheet had a k-factor of 0.21 at 25 ° f. The acrylic foam described in this invention has a much smaller and narrower cell size distribution than PU foam with a lower k-factor (better under adiabatic) due to a much higher density reduction.
b) Self-foaming PMMA based liquid resins can also be formulated using a method similar to that described in a). In this case, will
resin/MMA/unexpanded
The microsphere mixture is used in combination with a suitable free radical initiator package such that the subsequent reaction is exothermic
The microspheres expand. Thus, the proposed PMMA based liquid resin will foam and cure simultaneously. The formulation required low expansion temperature dry unexpanded Expancel microspheres such as Expancel820DU 40.
c) By vacuum infusion and wet moulding, with
The resin preparation has
Thermoplastic composites of unexpanded microspheres. In one experiment, 5 wt.% unexpanded was used
Addition of microspheres to
150, and 2 wt% of
AFR40 was used as initiator. The mixture was infused into a glass fiber mat reinforcement using standard vacuum infusion lay-up (i.e., peel ply, flow medium, adhesive tape, and bag). The process was carried out at room temperature and cured at room temperature for about 45 minutes. Once cured, the laminated composite is demolded and cut into sheets. Make a sliceSuspending in an oven at 200 deg.C for 5 minutes to allow
The particles expand. Another section was placed in a preheated steel mold with a set cavity thickness of 0.100 ". The mold was placed in a hydraulic press and pressure of about 50PSI was applied to close the mold and limit the expansion of the composite material to only a flat plane. Composite panels containing unexpanded particles (about 5 wt%) were successfully produced using a wet-moulding process. In the second heating stage, the Expancel particles expanded as expected and resulted in
The 40% density reduction in the composite part.
The application is as follows:
those skilled in the art can envision many uses for the composite thermoplastic (meth) acrylic foam articles of the present invention based on the description and examples. The foam composite may be used to form parts for many purposes, including but not limited to: automotive parts, ship parts, train parts, sports articles, aircraft parts, helicopter parts, spacecraft parts, rocket parts, photovoltaic module parts, wind turbine parts, furniture parts, structural parts, building parts, telephone or cell phone parts, computer or television parts, printer parts or photocopy parts.
Unlike polyurethane foams, this foaming technique does not require harmful diisocyanates and does not generate harmful VOCs for use in packaging materials. Foamable liquid slurries that are free of diisocyanates are desirable for electronic packaging.
Examples
Example 1: use of
Microspheres to obtain foamed sheets
20g of dry unexpanded
950DU80 microspheres were dispersed in 180g with a laboratory vibrator
190 (f).
190 is a mixture of MMA and acrylic copolymer with a viscosity of 100 cP. Once dispersed, 2g of
16 as initiator are mixed manually to
To the mixture, the mixture was then poured into 1/8 "thick glass molds and sealed, the molds were immersed in a water bath at 61 ℃ and polymerized for about 40 minutes, 1/8" thick translucent sheets were obtained, and the surface was smooth and glossy, the sheets were cut into 2 "× 2" slices and suspended in an air oven at 180 ℃ for 15 minutes to allow for
The microspheres expanded using this condition, a foamed sheet of 4 "× 4" with a thickness of 1/4 "was obtained, the foamed sheet had a 90% density reduction and a uniform cell size (108 ± 30 μm) with a k-factor of 0.21 at 25 ° f.
Example 2: by vacuum infusion
Microspheres to obtain composite parts
15g of dry unexpanded
950DU80 to which 285g of
150 and dispersed on a laboratory shaker. Once dispersed, will
AFR40 was added as initiator to the mixture at 6 g. The mixture was infused into the glass fiber mat reinforcement using standard vacuum infusion lay-up (i.e., peel ply, flowable media, adhesive tape, and bag). The process was carried out at room temperature and cured at room temperature for about 45 minutes. Once cured, the composite panels were cut into 1 "x 1" slices. Suspending a slice in an air oven at 200 deg.C to allow
The microspheres expand. Another section was placed in a preheated steel mold with a set cavity thickness of 0.100 ". The mold was placed in a hydraulic press and pressure of about 50PSI was applied to close the mold and limit the expansion of the composite material to only a flat plane. The density reduction obtained with both expansion methods is 30-40%.
Example 3: by liquid molding
Microspheres to obtain composite parts
3.3g of dry unexpanded
031DU40 microspheres were hand mixed to 63.2g
150, respectively. In the subsequent step, 1.3g of
AFR40 was added to the mixture as an initiator. The die was provided with two 1/8 "steel plates sandwiched between circular rubber spacers of 3.5mm diameter and a circular PPG MatVantage II chopped, stitched fiberglass mat was laid in the rubber ring between the steel plates. The mold was opened to pour the mixture onto the fiber mat and the mixture was spread evenly with a wooden tongue depressor. The mold was then placed in a hydraulic press preheated to 60 ℃ and the pressure was stepped from 100PSI to 100PSI during the cure profileGradually applied to 6000 PSI. After about 10 minutes, the composite panel was allowed to cure and cut into 1 "x 1" slices. One slice was suspended in an air oven preheated to 200 ℃. The other section was inflated using the same method, but cooled in a room temperature hydraulic press and pressure of about 50PSI was applied to minimize z-direction expansion. The density reduction is about 20-32%, and a smoother/glossier surface is obtained when the composite part is compressed while cooling. The resulting part is shown on the right side of fig. 1.
An embodiment of a method for implementing a "class a" surface:
as described above
Resin composition
The composite part is cured in the mold cavity. Once cured, the mold was opened slightly to allow some free space. Then heating the mould to
The extent to which the particles will begin to expand. This expansion pushes the resin efficiently towards the tool cavity walls. The mold is then cooled to stabilize the part, and then demolded.
The resulting part is shown on the left side of fig. 1.
One variation of the above process is to form the composite part in a mold, then demold and transfer to another mold with a slightly larger gap (e.g., 0.5mm overall), and then heat the part in the mold or before closing the mold. The mold is then closed to compress the parts within the mold for thickness uniformity. Examples of parts from unopened molds, and parts formed by first molding, then slightly opening the mold and further expanding.
This process involving mold opening and foaming, or mold transfer, is also used to melt process parts.
Claims (23)
1. A polymer foam composite comprising:
(a) a foamed polymeric thermoplastic (meth) acrylic matrix;
(b) the fibrous material used as a reinforcement is,
wherein the fibrous material comprises fibers having a fiber aspect ratio of at least 1000 or a fibrous material having a two-dimensional macrostructure, wherein the density of the foamed polymeric thermoplastic (meth) acrylic matrix is at least 5 wt. -%, preferably 10 wt. -%, preferably 20 wt. -%, preferably 30 wt. -%, more preferably 50 wt. -%, more preferably 70 wt. -%, more preferably 90 wt. -% lower than that of an unfoamed polymeric thermoplastic (meth) acrylic matrix of the same composition.
2. The polymer-foamed composite of claim 1, wherein the fibers are selected from the group consisting of: natural materials, plant fibers, wood fibers, animal fibers, mineral fibers, sisal, jute, hemp, flax, cotton, coconut fibers, banana fibers, wool, hair, aliphatic polyamides, aromatic polyamides, polyesters, polyvinyl alcohol, polyolefins, polyurethanes, polyvinyl chloride, polyethylene, unsaturated polyesters, epoxy resins, vinyl esters, mineral fibers, glass fibers, carbon fibers, boron fibers, silica fibers.
3. The polymer foam composite of claim 1, wherein the (meth) acrylic matrix polymer comprises at least 70% by weight methyl methacrylate monomer units.
4. The polymer foamed composite of claim 1, further comprising 0.1 to 10 weight percent of remaining expandable microspheres based on the weight of the polymeric thermoplastic (meth) acrylic matrix.
5. A liquid (meth) acrylic syrup comprising:
e) a (meth) acrylic polymer;
f) a (meth) acrylic monomer;
g) at least one initiator or initiating system to initiate polymerization of the (meth) acrylic monomer;
h) at least one kind of foaming agent,
the dynamic viscosity of the liquid (meth) acrylic syrup ranges from 10 to 10000, preferably from 50 to 5000, and advantageously from 100 to 1000mPa s.
6. The liquid (meth) acrylic syrup of claim 5 wherein the blowing agent comprises at least one chemical blowing agent.
7. The liquid (meth) acrylic syrup of claim 5 wherein the chemical blowing agent is selected from the group consisting of: azodicarbonamide, azobisisobutyronitrile, sulfonyl semicarbazide, 4-hydroxybenzene, barium azodicarboxylate, 5-phenyltetrazole, p-toluenesulfonyl semicarbazide, diisopropyliminodicarboxylate, 4' -oxybis (benzenesulfonylhydrazide), diphenylsulfone-3, 3' -disulfonylhydrazide, isatoic anhydride, N ' -dimethyl-N, N ' -dinitroterephthalamide, citric acid, sodium bicarbonate, monosodium citrate, anhydrous citric acid, trihydrazinotriazine, N ' -dinitrosopentamethylenetetramine, p-toluenesulfonylhydrazide, and blends thereof.
8. The liquid (meth) acrylic syrup of claim 5 wherein the blowing agent comprises expandable microspheres.
9. A thermoplastic (meth) acrylic foamed article comprising a (meth) acrylic matrix, the foamed article having a density reduction of at least 33%, at least 75%, at least 90% compared to an unfoamed (meth) acrylic article of the same composition.
10. The thermoplastic (meth) acrylate foamed article according to claim 9 comprising a thermoplastic (meth) acrylate matrix containing from 0.1 to 10 wt%, preferably from 1 to 5 wt% nanoparticles.
11. The thermoplastic (meth) acrylate foamed article of claim 10 wherein the nanoparticles are conductive nanoparticles.
12. The thermoplastic (meth) acrylate foamed article of claim 9 comprising a (meth) acrylic sheet having a k-factor at 25 ° f of less than 0.7, preferably less than 0.5, more preferably less than 0.25.
13. The thermoplastic (meth) acrylate foamed article of claim 9 having a class a surface as measured by astm e 340.
14. A method for foaming a (meth) acrylic foam, the method comprising the steps of:
a. admixing a blowing agent, a (meth) acrylic monomer, a (meth) acrylic polymer, and one or more initiators to form a liquid (meth) acrylic syrup having a dynamic viscosity in the range of from 10 mPas to 10000 mPas, preferably from 50 mPas to 5000 mPas, and advantageously from 100 mPas to 1000 mPas,
b. the structure is formed by polymerization of a liquid (meth) acrylic syrup.
15. The method of claim 14, wherein the foaming and polymerization processes occur simultaneously to form the foamed structure.
16. A method according to claim 14, wherein the structure is foamed after polymerisation by the addition of energy capable of expanding a blowing agent.
17. The method of claim 14, wherein the blowing agent comprises at least one chemical blowing agent.
18. The method of claim 14, wherein the foaming agent comprises expandable microspheres.
19. The method of claim 14, wherein the structure formation is performed by cell casting, solid state casting, vacuum infusion, pultrusion, wet molding, resin transfer molding, compressed resin transfer molding, lay-up/spray coating, or filament winding.
20. The method of claim 14, wherein the liquid (meth) acrylic syrup is combined with long fibers having a fiber aspect ratio of at least 1000 or a fibrous material having a two-dimensional or three-dimensional macrostructure prior to polymerization.
21. The method of claim 14, wherein the combination of long fibers and liquid (meth) acrylic syrup is achieved by gravure coating, immersion dip coating, slot die coating, curtain coating, or gap coating.
22. A method for forming a (meth) acrylic foam having an improved surface appearance as measured by astm e340, comprising the steps of:
a) forming a thermoplastic (meth) acrylic foamed article in a mold, wherein the thermoplastic (meth) acrylic foamed article comprises expandable microspheres;
b) curing the article;
c) enlarging the size of the mold by slightly opening the mold or moving the cured article into a slightly larger mold;
d) adding additional heat to the article, causing it to expand further to fill the larger mold;
e) allowing the article to cool; and
f) the article is demolded.
23. The polymer foamed composite of claim 1, wherein the material is an article for use as an automotive part, a ship part, a train part, a sporting article, an airplane part, a helicopter part, a spacecraft part, a rocket part, a photovoltaic module part, a wind turbine part, a furniture part, a structural part, a building part, a telephone or cell phone part, a computer or television part, a printer part, or a photocopy part.
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| US62/593,460 | 2017-12-01 | ||
| PCT/US2018/062944 WO2019108721A1 (en) | 2017-12-01 | 2018-11-29 | Foamable acrylic composition |
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| CN111566154A true CN111566154A (en) | 2020-08-21 |
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| EP (1) | EP3717554A4 (en) |
| JP (2) | JP7419232B2 (en) |
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| CN (1) | CN111566154A (en) |
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| CN116496489A (en) * | 2023-06-30 | 2023-07-28 | 富海(东营)新材料科技有限公司 | Preparation process of multifunctional semi-aromatic nylon |
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| CN111566154A (en) * | 2017-12-01 | 2020-08-21 | 阿科玛股份有限公司 | Foamable acrylic composition |
| EP3883734A4 (en) * | 2018-11-19 | 2022-08-31 | Arkema France | Acrylic composites with improved surface properties |
| JP2022543318A (en) * | 2019-08-08 | 2022-10-11 | エボニック オペレーションズ ゲーエムベーハー | Process for producing polymethyl methacrylate rigid foam as core material in rotor blade and boat construction for wind turbines |
| EP4284861A1 (en) | 2021-01-27 | 2023-12-06 | Zephyros Inc. | Low odor heat-expandable materials |
| FR3141180A1 (en) | 2022-10-25 | 2024-04-26 | Arkema France | (Meth)acrylic composition, foam material obtained from such a composition, process for producing said composition and said foam, and uses thereof |
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Also Published As
| Publication number | Publication date |
|---|---|
| JP2023155325A (en) | 2023-10-20 |
| EP3717554A1 (en) | 2020-10-07 |
| JP2021504549A (en) | 2021-02-15 |
| KR20200085910A (en) | 2020-07-15 |
| WO2019108721A1 (en) | 2019-06-06 |
| US20230279214A1 (en) | 2023-09-07 |
| CA3083524A1 (en) | 2019-06-06 |
| BR112020010880A2 (en) | 2020-11-10 |
| JP7419232B2 (en) | 2024-01-22 |
| MX2020005744A (en) | 2020-08-20 |
| US20200385564A1 (en) | 2020-12-10 |
| US12012510B2 (en) | 2024-06-18 |
| EP3717554A4 (en) | 2022-01-12 |
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